因此，本發明之一個目的是提供含有金屬粒子(特別是奈米金屬粒子，較佳為貴金屬粒子)之塗覆組成物，其允許以簡單方式藉助廣泛的印刷法或塗覆法來施加該塗覆組成物，及以一步驟方法產生在矽化型基材上之高裝飾平光金屬元件，其為機械安定的、耐刮刻的及耐腐蝕的。應該可以將奈米銀粒子作為唯一金屬粒子，藉此避免腐蝕的缺點。本發明之另一個目的是顯示可怎麼使用此等塗覆組成物。本發明之另一個目的是提供在矽化型表面上之平光的吸引人之裝飾塗層及其產生方法。 本發明之目的透過下列來解決：一種塗覆組成物，其包含： 以加到100%的塗覆組成物重量為基準計， A) 5至40重量%之展現在30至300 nm範圍內的d50
值之金屬粒子，該d50
值係利用體積相關雷射繞射法測得，其中該金屬粒子係選自由下列所組成之群組：Ag、Au、Ru、Ir、Pd、Pt、Cu、Nb、或含有上述金屬中至少一者的合金， B) 1至30重量%之一或多種元素的有機化合物，該一或多種元素係選自由下列所組成之群組：Si、Ge、Nb、Sn、Zn、Zr、Ti、Sb、Al、Bi、鹼金屬或鹼土金屬，先決條件是至少一種含有氧或氮之有機Si化合物存在， C) 5至25重量%之黏合劑，其含有至少一種選自聚乙烯縮醛類(polyvinylacetales)的群組之化合物， D) 10至70重量%的溶劑， E) 0至10重量%之流變改性添加劑，和 F) 0至5重量%之至少一種金屬鹽化合物，其中該金屬係選自由下列所組成的群組：Co、Ni、Cu、Cr、Fe、Mn、Au、Rh、Ru、Ir、Os及Pt。 本發明之目的還透過下列來解決：上述塗覆組成物的用途，其係用於製造在展現瓷(porcelain)、瓷(china)、骨瓷、陶瓷、玻璃或琺瑯表面之物件上的金屬、金色或銀色裝飾元件。 此外，本發明之目的透過下列來解決：一種在基材上的含有金屬粒子之固體塗層，其包含以該固體塗層重量為基準計至少60重量%的至少一種金屬之金屬粒子，該至少一種金屬係選自由下列所組成的群組：Ag、Au、Ru、Ir、Pd、Pt、Cu、Nb、或含有上述金屬中至少一者之合金，並包含以該固體塗層重量為基準計至少5重量%的玻璃基質，該玻璃基質由SiO2
組成或包含SiO2
與鹼金屬氧化物、鹼土金屬氧化物、GeO2
、Nb2
O3
、SnO、SnO2
、ZnO、ZrO2
、TiO2
、Al2
O3
、Bi2
O3
及Sb2
O3
中至少一者。 此外，本發明之目的透過下列來解決：一種用於產生在基材上的含有金屬之固體塗層的方法，由此將如上述之含有金屬粒子的塗覆組成物施加於基材上且隨後在500℃至1250℃範圍中之溫度下熱處理。 根據本發明之塗覆組成物含有成分A)以該塗覆組成物總重量為基準計5至40重量%、特別是20至30重量%的展現在30至300 nm範圍內、較佳為在150至300 nm範圍內的d50
值之奈米金屬粒子，而該d50
值係利用根據ISO 13320:2009的體積相關雷射繞射法測得。 該奈米金屬粒子係選自由下列所組成之群組：Ag、Au、Ru、Ir、Pd、Pt、Cu、Nb、或含有上述金屬中至少一者的合金。在該塗覆組成物中可能含有單獨之該奈米金屬粒子(只有一種金屬粒子)或含有二或多種上述金屬粒子的混合物。 較佳地，該奈米金屬粒子係選自由下列所組成的群組之貴金屬粒子：Ag、Au、Ru、Ir、Pd、Pt、或含有上述貴金屬中至少一者的合金。最佳的，該奈米粒子是銀奈米粒子或銀合金奈米粒子，該合金含有以該合金總重量為基準計至少50重量%之銀。 本發明之一個大優點是只含有銀奈米粒子且無另外的金屬粒子之塗覆組成物耐腐蝕幾個月且可用於產生在矽化型表面上的平光銀色裝飾元件，其也保持耐腐蝕性。 除了奈米金屬粒子之外，本發明的塗覆組成物還含有成分B)以該塗覆組成物總重量為基準計1至30重量%，特別是1至15重量%，之一或多種元素的有機化合物，該一或多種元素係選自由下列所組成之群組：Si、Ge、Nb、Sn、Zn、Zr、Ti、Sb、Al、Bi、鹼金屬與鹼土金屬，先決條件是至少一種含有氧或氮之有機Si化合物存在。 在基材上的所得之固體塗層中個別化合物具有玻璃形成物的作用，由於該化合物在熱處理後分解成對應金屬氧化物。 成分B)之主要組分是必須存在的含有氧或氮之矽化合物。其可包含在本發明之塗覆組成物中作為上述成分B)的有機金屬化合物之外的唯一有機化合物，但是也可和除了有機Si化合物之外的上述有機化合物中一或多者一起存在。該含有氧或氮之有機Si化合物在含有氧的氣氛中於熱分解後形成以Si-O為基礎之網絡。為了可用於此目的，該對應含有氧或氮的有機Si化合物在分解前不能蒸發。此外，烷氧基矽烷類雖然含有Si與氧，但卻無法用於此目的，由於其在不可避免有痕量水存在於塗覆組成物中的情況下容易經歷水解。因此，通用式1、式2或式3之聚矽氮烷化合物、聚矽氧烷化合物與聚矽氧樹脂是該含有氧或氮之有機矽化合物B)的最好選擇。而 R1
是選自由下列所組成的群組之基團：H、C1
-C18
烷基、C5
-C6
-環烷基、經取代或未經取代的苯基、OH、OC1
-C18
烷基、NH2
及N(C1
-C18
烷基)2
； R2
、R3
與R5
彼此獨立地是選自由下列所組成的群組之基團：H、C1
-C18
烷基、OH、OC1
-C18
烷基、NH2
、N(C1
-C18
烷基)2
、OSi(R1
)3
及N=SiR1
； R4
是選自由下列所組成的群組之基團：H、C1
-C18
烷基、C5
-C6
-環烷基及苯基； X 是O或N的基團；和 m與n彼此獨立地是選自在1至100範圍內的數目之整數； 先決條件是各種材料的沸點超過150℃。 例如，Durazan 1066(CAS-No.346577-55-7)或聚二甲基矽氧烷(CAS-No.9016-00-6)可有利地作為在本塗覆組成物中的含有氧或氮之有機Si化合物B)。 此外，通用式4之矽倍半氧烷聚合物也有利地有用：而 R1
與R2
是彼此相同或不同的基團且是選自由下列所組成的群組：氫、烷基、烯、環烷基、芳基、伸芳基與烷氧基，和 m與n彼此獨立地是選自在1至100範圍內的數目之整數， 先決條件是各種材料的沸點超過150℃。 此外，除了該含有氧或氮的有機Si化合物之外，選自由Ge、Nb、Sn、Zr、Ti、Sb、Al、Bi、鹼金屬及/或鹼土金屬所組成的群組之元素的有機化合物也可存在於本發明之塗覆組成物中。這些有機化合物可為對應元素的醇鹽、羧酸鹽、檸檬酸鹽、乙醯丙酮酸鹽及/或酒石酸鹽。上述有機化合物如果有的話是以成分B)之化合物總重量為基準計1至30重量%的量存在於本塗覆組成物中。特別地，含有機鹼金屬化合物量及/或含有機鹼土金屬化合物量不應超過以成分B)的化合物總重量為基準計10重量%。 較佳地，經查式5之醇鹽係適合的：而 Met 是選自由下列所組成的群組：Ge、Nb、Sn、Zr、Ti、Sb、Al、Bi、鹼金屬及鹼土金屬， Z 是選自由下列所組成的群組：CO、SO2
與SO3
； P 是0或1， R6
是選自由下列所組成的群組之基團：C1
-C18
烷基、C5
-C6
-環烷基及經取代或未經取代的苯基。 根據本發明之塗覆組成物也包含以該塗覆組成物總重量為基準計5至25重量%、較佳為5至15重量%的黏合劑。 出乎意料地，本案發明人找到黏合劑，其含有至少一種選自聚乙烯縮醛類的群組之化合物，最能夠提供可有利地用於幾種印刷法與塗覆法的本種塗覆組成物。該黏合劑在很大程度上決定了該塗覆組成物在印刷法過程中的黏度。儘管該塗覆組成物之黏度必須夠低以在各種印刷法或塗覆法中適於印刷或塗覆，然而個別塗層或印刷層在施加後必須在基材上保持安定而不分散超出經塗覆的表面積。此外，該黏合劑在熱處理在本塗覆組成物之施加範圍內的所得之塗層或印刷層後必須完全燃燒。聚乙烯縮醛類之群組滿足本塗覆組成物的這些要求。聚乙烯縮醛類是聚乙烯甲醛、聚乙烯乙醛與聚乙烯丁醛。 聚乙烯縮醛類特性隨其縮醛化程度變動。聚乙烯丁醛類結果是本塗覆組成物之最好選擇。因此，聚乙烯丁醛類較佳地作為在本塗覆組成物中的黏合劑。尤其有用的是具18至24重量%之含OH量的聚乙烯丁醛類。 Kuraray的聚乙烯丁醛類(在商標Mowital®與 Pioloform®下販售)可被有利地使用，特別是分別具有約40.000 g/mol與約55.000 g/mol之平均莫耳質量並各自展現約70℃的玻璃轉化溫度之Mowital® B 45 H與Mowital® B 60 H，而Mowital® B 60 H是優選。不言而喻，具有相當的特性之另外公司的聚乙烯丁醛類也有用。 含有聚乙烯縮醛之黏合劑可含有以該黏合劑總重量為基準計到至少50重量%的聚乙烯縮醛，或可由至少一種選自聚乙烯縮醛類之群組的化合物組成。較佳地，該黏合劑包含聚乙烯丁醛。在本發明之最佳實施態樣中，該黏合劑是由聚乙烯丁醛組成。 最佳的，該黏合劑是由具有在30.000至60.000 g/mol範圍中之平均莫耳質量及18至24重量%的含OH量之聚乙烯丁醛組成。 本發明之塗覆組成物還含有10至70重量%，較佳為40至70重量%，的溶劑。該溶劑有利地是有機溶劑。不幸地，痕量水通常可能不避免以達到等於零之含量，儘管在本塗覆組成物中的溶劑最好只含有有機溶劑。因此，用於本塗覆組成物之有機溶劑可含有以該溶劑重量為基準計0至最多10重量%的含量之水。在使用有機溶劑混合物情況下，較佳的是，各種有機溶劑可具有以各種有機溶劑重量為基準計在0至最多10重量%範圍內之含水量，由此在該溶劑混合物中的最大水量不超過10重量%。就單一有機溶劑或有機溶劑混合物而言，視情況而定，對所用的各種單一有機溶劑而言，該含水量較佳為0至5重量%，更佳為0至3重量%。 原則上，能夠溶解固體化合物(除金屬粒子外)且在熱處理在矽化型基材上的所得之塗層的溫度下蒸發而無殘留物的所有有機溶劑皆可用於本塗覆組成物。實例是醇類比如乙醇、異丙醇、己醇或2-乙基己醇、乙氧基乙醇、甲氧基乙醇、甲氧基丙醇及上述醇類中至少二者之混合物。此外，多元醇類的醚類特別有用，尤其是三-丙二醇-一甲醚(TPM)與二-丙二醇-一甲醚(DPM)。最佳為2-乙基己醇、三-丙二醇-一甲醚(TPM)與二-丙二醇-一甲醚(DPM)。所有溶劑皆可以唯一溶劑或以含有幾種溶劑的混合物形式被使用。 隨意地，非醇溶劑也可以該溶劑混合物重量為基準計1到最多40重量%的量存在於該溶劑混合物中，例如但不限於醚類像二烷基丙二醇、二㗁烷或THF、芳香族溶劑類像二甲苯、飽和與不飽和脂族烴類像萜烯溶劑類與石油腦、醯胺類像N-乙基吡咯啶酮、酯類像苯甲酸乙酯或脂肪酯類。 藉由改變溶劑的量，可將根據本發明之塗覆組成物的黏度調整成有用並適合於對應塗覆技術或印刷技術的值。本發明之一個大優點是該塗覆組成物可用於幾種塗覆技術或印刷技術，由此可產生濃塗覆組成物，其可藉由簡單地調整溶劑含量來稀釋成所要求的值，從而對幾種塗覆技術或印刷技術(包括噴墨印刷法)有用。 除了上述必需成分之外，本發明的塗覆組成物還可在必須以非常特別之方式進一步調整該塗覆組成物的黏度情況下隨意地包含流變改性劑。該流變改性劑可以該塗覆組成物重量為基準計0至10重量%之量存在。較佳地，使用0至8重量%，特別是0至5重量%的量。用於本塗覆組成物之流變改性劑可選自由下列所組成的群組：松油、蓖蔴油、脂肪酸、脂肪酸衍生物及天然蠟或合成蠟。 脂肪酸實例是亞麻油酸、油酸、硬脂酸、棕櫚酸、肉豆蔻酸、月桂酸及癸酸。脂肪酸衍生物也是有用的。 天然蠟與合成蠟實例是C19
至C30
烴類之褐煤蠟(montane wax)、棕櫚蠟(canauba wax)、褐蠟(tan wax)、松香蠟(collophonium wax)像松香酸或松香、或聚烯烴蠟像Clariant的Ceridust®蠟等。 此外，根據本發明之塗覆組成物還可隨意地含有至少一種金屬鹽化合物，其中該金屬鹽係選自由下列所組成的群組：Co、Ni、Cu、Cr、Fe、Mn、Au、Rh、Ru、Ir、Os與Pt。該金屬鹽化合物可以該塗覆組成物重量為基準計0至5重量%、較佳為0至3重量%、特別是0.1至1.5重量%的量存在。該金屬鹽有下列功能：調整在所得之經塗覆產品中的所得之金屬層的顏色，及/或在後續塗覆步驟中促進各塗覆組成物黏著於基材。該金屬鹽在經塗覆之基材上的塗覆組成物之最後熱處理下分解成對應金屬氧化物及/或金屬。 較佳地，將有機金屬鹽類用於根據本發明之塗覆組成物。實例是樹脂酸鹽、硫樹脂酸鹽(sulforesinate)、硫醇鹽、羧酸鹽及醇鹽。該金屬鹽類通常是以其在上述有機溶劑中任一者的溶液形式被使用。 不言而喻，上述所有重量百分率在指的是上述塗覆組成物之組分A)至F)情況下，是指加到100重量%的該塗覆組成物總重量。 此外，根據本發明之塗覆組成物還可含有通常用來產生在矽化型基材上的金屬塗層之另外的添加劑，比如界面活性劑、消泡劑、有機顏料及填料、另外之觸變劑等。在使用另外的添加劑情況下，這些添加劑之重量百分率也被選擇到組分A)至F)與該另外的添加劑之總和加到100重量%的程度。 本發明也關於一種用於產生上述塗覆組成物之方法，其中將化合物A)至F)互相均勻地混合，由此達到備用(ready-to-use)塗覆組成物。較佳地，製備黏合劑的溶液並連續地加入其他組分(較佳為和該溶劑中一或多者混合)。視需要而定，還可加入上述另外的添加劑中一或多者。該混合較佳地利用轉子定子均質機或Speedmixer®在環境溫度下進行。在某些情況下，除氣可能很重要，視所用溶劑的量與種類而定。 本發明之一大優點是用於產生上述塗覆組成物的方法盡可能簡單。僅混合組分就足以達到安定之塗覆組成物，其可在沒有固體組分的降解、分解或沉降下儲存於密閉容器中至少六個月。視所用溶劑、流變改性劑及/或其他觸變劑的含量而定，所製得之塗覆組成物可用於不同塗覆法或印刷法(包括噴墨印刷法)。因此，濃式本塗覆組成物可在幾種塗覆法或印刷法中供客戶施加，由於溶劑的含量後來在客戶處也可被調整。 本發明也關於上述塗覆組成物之用途，其係用於製造在展現比如瓷(porcelain)、瓷(china)、骨瓷、陶瓷、玻璃或琺瑯的矽化型表面之物件上的金屬、金色或銀色裝飾元件。 為了達到如上述之在矽化型表面上的此等金屬元件，必須將根據本發明之塗覆組成物施加於物件的矽化型表面而後進一步處理。 因此，本發明也關於一種用於產生在基材上的含有金屬之塗層的方法，由此將如上述所構成之塗覆組成物施加於該基材上且隨後在500℃至1250℃範圍中的溫度下處理。該處理是在含有氧之氣氛中進行。 根據本發明，具有上述矽化型表面的基材是展現瓷(porcelain)、瓷(china)、骨瓷、陶瓷、玻璃或琺瑯的表面之物件。該物件種類本身沒有限制。原則上，可使用藉由具有在其表面上的本塗覆組成物之化合物A)所提到的金屬之金屬層而使裝飾或功能豐富的所有物件。實例是家用或專業應用等之磁磚、建築元件、玻璃與瓷。 該塗覆組成物可直接或藉助轉移媒介而施加於該基材表面上。 直接施加能藉由本領域技術人員熟悉的任何方法來進行。將該塗覆組成物施加於該基材上能藉由將該基材浸入該塗覆組成物中或藉由任何塗覆法或印刷法來進行，該塗覆法或印刷法比如簾塗法、滾筒塗法、旋塗法、含浸法、澆注法、滴塗法、噴射法、噴霧法、刮刀塗法、塗裝法或印刷法，而該印刷法可為噴墨印刷法、網印法、凹版印刷法、平版印刷法或移印法，且該塗裝法為筆塗裝法、毛刷塗裝法等。 上述塗覆法之選擇取決於基材種類與尺寸及被施加於該基材上的塗層種類。不言而喻，該塗覆組成物之黏度由於所需要的塗覆技術而必須被調整。由於本塗覆組成物之黏度在大多數情況下可藉由改變個別溶劑的量被簡單可變地調整，根據本發明之濃塗覆組成物可作為用於多於一種的施加技術之基底組成物。 較佳的印刷法是網印法、凹版印刷法、移印法(pad printing)及噴墨印刷法。藉助刷子或筆的印刷法也是有利可用的。 將該塗覆組成物施加於該基材上也可藉由直接方法進行，亦即藉由第一步將該塗覆組成物施加於轉移媒介上，第二步藉助經預塗覆該根據本發明之塗覆組成物的該轉移媒介而將該塗覆組成物施加於該基材上。該轉移媒介可由經預塗覆本塗覆組成物並經乾燥之聚合物或紙載體(例如以印花形式)構成。然後藉由將該經預塗覆的載體定位於該基材上並移除該聚合物或紙載體來將該塗覆組成物施加於該基材上。在這種情況下熱處理是在將該塗覆組成物施加於該基材上之後進行，而非在將該塗覆組成物施加於該聚合物或紙載體上之後進行。 該基材能具有允許將該塗覆組成物施加於該基材的任何形狀。平坦基材比如膜類、板類及片類和任何形狀(像球形或錐形或任何其他有用的三維形狀)之三維基材一樣有用。該基材可為緻密體或空心體，其具有經本發明的塗覆組成物覆蓋的瓷(porcelain)、瓷(china)、骨瓷、陶瓷、玻璃或琺瑯外及/或內矽化型表面。 該基材之矽化型表面較佳地含有至少一個上面可被施加該塗覆組成物的連續區。經該塗覆組成物覆蓋之區域的形狀可為下列形式之任何合適形狀：規則或不規則圖案、線條、幾何形狀(比如圓形、正方形、矩形等)、相片、標誌、條碼等。該經覆蓋該塗覆組成物的基材區域之大小與形狀只受限於所用的塗覆法或印刷法種類及/或該基材本身之幾何形狀。本塗覆法允許在該基材上製造具有非常精細的線徑之圖案。 該經塗覆的區域之大小是在0.5 mm2
至10 m2
範圍內，特別是在10 mm2
至5 m2
範圍內，及最佳在100 mm2
至1 m2
範圍內。也可以是0.01 mm至10 cm、特別是0.1 mm至1 cm的線徑。 當完成根據本發明之塗覆法時達到在基材上的固體塗層，其中該塗層含有連續緻密金屬層，其包含在該塗覆組成物之組分A)下提到的奈米金屬粒子，而該奈米金屬粒子至少部分藉由玻璃基質來包封。此金屬層係藉由玻璃面塗層來覆蓋。該玻璃基質及該玻璃面塗層含有在該塗覆組成物之組分B)下提到的金屬的金屬氧化物及隨意的在組分F)下提到之金屬的金屬或金屬氧化物。至少，該玻璃基質及該玻璃面塗層含有由矽原子與氧原子製成之網絡。剩餘氮原子也可能存在。該面塗層保護該金屬層並防止其腐蝕及/或機械分解或化學分解，而包封該金屬粒子的該基質使該奈米金屬粒子能夠黏著於該基材。 儘管根據本發明之塗覆組成物被施加於該基材並在進行熱處理後自動地包括如上述的保護該金屬層之面塗層，但是可能希望或有利地藉由一或多個另外的保護層來覆蓋所得之固體塗層。因此，本方法還隨意地包括一個方法步驟，其中含有金屬粒子的塗覆組成物可進一步部分地或完全地覆蓋以另外的保護層。此方法步驟可在熱處理所得之層堆疊前進行，或甚至可在熱處理在基材上之含有金屬粒子的塗覆組成物後再進行。 本發明也關於在基材上的含有金屬粒子之固體塗層，其包含以該固體塗層重量為基準計至少60重量%的至少一種金屬之金屬粒子，該至少一種金屬係選自由下列所組成的群組：Ag、Au、Ru、Ir、Pd、Pt、Cu、Nb、或含有上述金屬中至少一者之合金，及包含以該固體塗層重量為基準計至少5重量%之玻璃基質，該玻璃基質由SiO2
組成或包含SiO2
與鹼金屬氧化物、鹼土金屬氧化物、GeO2
、Nb2
O3
、SnO、SnO2
、ZnO、ZrO2
、TiO2
、Al2
O3
、Bi2
O3
及Sb2
O3
中至少一者。 該金屬粒子是和該塗覆組成物有關的如上述之組分A)的奈米金屬粒子。 該玻璃基質之含量較佳為以該固體塗層重量為基準計在5至40重量%範圍內，特別是在5至20重量%範圍內。從而，在該基材上的含有金屬粒子之固體塗層中的含金屬粒子量較佳為至少80%，亦即在該固體塗層總重量之80至95重量%範圍內。 如果該玻璃基質含有多達以在該基材上之該固體塗層重量為基準計最多5重量%的鹼金屬氧化物及/或鹼土金屬氧化物是有利的，由於這樣低濃度之鹼金屬氧化物及/或鹼土金屬氧化物可改善和耐刮性與長期暴露於蒸氣的耐用性有關的所得之塗層的機械特性。 如果存在，根據該塗覆組成物之組分F)的金屬鹽之分解產物算在含玻璃基質量上而非算在含金屬粒子量上。因此，該玻璃基質還可另外含有一或多種金屬或金屬氧化物，該金屬選自下列群組：Co、Ni、Cu、Cr、Fe、Mn、Au、Rh、Ru、Ir、Os及Pt。 較佳地，該玻璃基質含有Cu、Au、Rh及/或Ru之金屬或金屬氧化物，其係由化合物F)的組分衍生。 在本發明之一個較佳實施態樣中，在該基材上的含有金屬粒子之固體塗層中的該金屬粒子是由一或多種選自下列所組成之群組的貴金屬構成：Ag、Au、Ru、Ir、Pd、Pt、或含有上述貴金屬中至少一者的合金。 最佳的實施態樣，是其中在基材上的含有金屬粒子之固體塗層僅含有銀金屬粒子或含銀合金金屬粒子，該合金具有以其重量為基準計至少50重量%之含銀量。 如上述在某種程度上的說明，在基材上的含有金屬粒子之固體塗層是由位於彼此之上的二層構成，由此第一層直接位於基材上並構成緻密堆積之金屬層，其包含展現在50至300 nm範圍內的d50
值之經聚集的金屬粒子，該d50
值係利用體積相關雷射繞射法測得，其中該金屬粒子係選自由下列所組成之群組：Ag、Au、Ru、Ir、Pd、Pt、Cu、Nb、或含有上述金屬中至少一者的合金，且其中第二層位於該第一層之上並為至少包含SiO2
的玻璃樣層(glass-like layer)。 該緻密堆積之金屬層構成連續層，其中該金屬粒子仍可被認為是展現在50至300 nm範圍內的d50
值之粒子，但是經聚集且部分融合在一起且至少部分地藉由玻璃基質來包封，該玻璃基質是由和在該金屬層之上的玻璃樣層相同之成分構成。 保護層位於該金屬層之上，該保護層具有玻璃樣結構並由只包含SiO2
的玻璃基質構成，或由包含SiO2
與一或多種金屬氧化物之玻璃基質構成，該一或多種金屬氧化物選自下列群組：鹼金屬氧化物、鹼土金屬氧化物、GeO2
、Nb2
O3
、SnO、SnO2
、ZnO、ZrO2
、TiO2
、Al2
O3
、Bi2
O3
及Sb2
O3
。該保護層如果存在還可含有組分F)的分解產物，更確切地講一或多種選自下列群組之金屬或金屬氧化物：Co、Ni、Cu、Cr、Fe、Mn、Au、Rh、Ru、Ir、Os及Pt。 在本發明之一個最佳實施態樣中，根據本發明之在基材上的固體塗層是由下列構成：直接位於該基材上之金屬層，其包含銀粒子或具有以合金重量為基準計至少50重量%的含銀量之合金粒子，其展現如上述的在50至300 nm範圍內的d50
值，及在該金屬層之上的含有SiO2
與銠之玻璃樣層。以加到100%的塗層重量為基準計，該金屬(亦即Ag或Ag合金)之量是至少85重量%，SiO2
的量是至少3重量%，及銠之量是最多0.5重量%。 如上述之玻璃樣層覆蓋該金屬層並使該金屬層能夠免於腐蝕及機械分解或化學分解。此外，該玻璃樣層提供某種耐刮性給下方的該金屬層。該玻璃樣層之保護特性夠強甚至足以防止銀奈米粒子(通常容易受到強烈腐蝕)發生腐蝕。從而，第一次可以將銀奈米粒子用於產生在具有根據本發明之塗覆組成物的陶瓷、玻璃、磁磚等之上的閃亮銀裝飾。 上面有固體塗層的基材是展現例如瓷(porcelain)、瓷(china)、骨瓷、陶瓷、玻璃或琺瑯表面的外矽化型表面之物件。不言而喻，整個物件可由上述材料中的一者構成，但是只具有矽化型表面之物件，其中該物件主體是由不同材料構成，也應該包括在本發明中。當然，該物件表面及其主體必須經受得起上述熱處理的溫度。該物件本身之形狀與大小沒有限制。該矽化型表面可為該物件的外表面或內表面(例如對空心物件而言)。 本發明允許在一個塗覆步驟中用平光或消光(視情況而定)的金屬層來塗覆物件的矽化型表面，該金屬層展現銀色或金色並被保護免於化學分解或機械分解或腐蝕。甚至該塗覆組成物本身具有長儲存壽命，亦即耐腐蝕與分解至少六個月。所用之奈米金屬粒子可在使用前製成合適大小且不必像往常一樣在被覆蓋的表面上就地產生在矽化型表面上的金色裝飾。由於甚至奈米銀粒子在本塗覆組成物中夠安定且特別耐腐蝕，故可以將銀(而非鈀與鉑)用於產生在矽化型物件(比如個人用途或工業用途之陶瓷、玻璃與磁磚)上的銀色裝飾，因而改善在產生個別商品方面之成本控制。 本發明在下列實施例中會被詳細說明，但是不應受到該實施例限制。Accordingly, it is an object of the present invention to provide a coating composition containing metal particles, especially nano metal particles, preferably precious metal particles, which allows the coating to be applied in a simple manner by a wide range of printing methods or coating methods. The coating composition, and the highly decorative flat metal element produced on the siliconized substrate in a one-step method, are mechanically stable, scratch-resistant, and corrosion-resistant. It should be possible to use nano silver particles as the sole metal particles, thereby avoiding the disadvantages of corrosion. Another object of the invention is to show how such coating compositions can be used. Another object of the present invention is to provide an attractive decorative coating with flat light on a silicified surface and a method for producing the same. The object of the present invention is solved by the following: A coating composition comprising: based on the weight of the coating composition added to 100%, A) 5 to 40% by weight of the coating composition exhibiting in the range of 30 to 300 nm the d 50 value of the metal particles, the d 50 value of the system related to the volume measured using a laser diffraction method, wherein the group consisting of metal particles selected from the group consisting of the following: Ag, Au, Ru, Ir , Pd, Pt, Cu , Nb, or an alloy containing at least one of the above metals, B) An organic compound of one or more elements of 1 to 30% by weight, the one or more elements being selected from the group consisting of: Si, Ge, Nb , Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metal or alkaline earth metal, the prerequisite is the presence of at least one organic Si compound containing oxygen or nitrogen, C) 5 to 25% by weight of a binder, which contains at least A compound selected from the group of polyvinylacetales, D) 10 to 70% by weight of a solvent, E) 0 to 10% by weight of a rheology modifying additive, and F) 0 to 5% by weight of a compound At least one metal salt compound, wherein the metal is selected from the group consisting of: Co, Ni Cu, Cr, Fe, Mn, Au, Rh, Ru, Ir, Os and Pt. The object of the present invention is also solved by the following: the use of the coating composition described above, which is used for manufacturing metal on objects exhibiting porcelain, china, bone china, ceramics, glass or enamel surface, Gold or silver decorative elements. Furthermore, the object of the present invention is solved by the following: a solid coating containing metal particles on a substrate, comprising at least 60% by weight of metal particles of at least one metal based on the weight of the solid coating, the at least A metal system is selected from the group consisting of: Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or an alloy containing at least one of the above metals, and includes a weight based on the weight of the solid coating at least 5 wt% of the glass substrate, the glass substrate composed of SiO 2 or SiO 2 containing alkali metal oxides, alkaline earth metal oxides, GeO 2, Nb 2 O 3 , SnO, SnO 2, ZnO, ZrO 2, TiO 2 , Al 2 O 3 , Bi 2 O 3 and Sb 2 O 3 . Furthermore, the object of the present invention is solved by a method for producing a metal-containing solid coating on a substrate, whereby a coating composition containing metal particles as described above is applied to the substrate and then Heat treatment at a temperature in the range of 500 ° C to 1250 ° C. The coating composition according to the present invention contains ingredient A) 5 to 40% by weight, particularly 20 to 30% by weight, based on the total weight of the coating composition, exhibiting in the range of 30 to 300 nm, preferably in the range of Nano metal particles with a d 50 value in the range of 150 to 300 nm, and the d 50 value is measured using a volume-dependent laser diffraction method according to ISO 13320: 2009. The nano metal particles are selected from the group consisting of Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or an alloy containing at least one of the above metals. The coating composition may contain the nano metal particles alone (only one kind of metal particles) or a mixture containing two or more of the above metal particles. Preferably, the nano metal particles are noble metal particles selected from the group consisting of: Ag, Au, Ru, Ir, Pd, Pt, or an alloy containing at least one of the above noble metals. Most preferably, the nano particles are silver nano particles or silver alloy nano particles, and the alloy contains at least 50% by weight of silver based on the total weight of the alloy. A big advantage of the present invention is that the coating composition containing only silver nano particles and no additional metal particles is resistant to corrosion for several months and can be used to produce flat silver decorative elements on a silicified surface, which also maintains corrosion resistance . In addition to nano metal particles, the coating composition of the present invention also contains component B) 1 to 30% by weight, particularly 1 to 15% by weight, based on the total weight of the coating composition, one or more elements An organic compound of one or more elements selected from the group consisting of Si, Ge, Nb, Sn, Zn, Zr, Ti, Sb, Al, Bi, alkali metals and alkaline earth metals, the prerequisite is at least one Organic Si compounds containing oxygen or nitrogen are present. Individual compounds in the resulting solid coating on the substrate have the effect of glass formations because the compounds decompose into corresponding metal oxides after heat treatment. The main component of ingredient B) is a silicon compound containing oxygen or nitrogen which must be present. It may be included in the coating composition of the present invention as the only organic compound other than the organometallic compound of the above-mentioned component B), but may also exist together with one or more of the above-mentioned organic compounds other than the organic Si compound. The organic Si compound containing oxygen or nitrogen forms a network based on Si-O after thermal decomposition in an atmosphere containing oxygen. In order to be useful for this purpose, the corresponding organic Si compound containing oxygen or nitrogen cannot be evaporated before decomposition. In addition, alkoxysilanes, although containing Si and oxygen, cannot be used for this purpose because they are susceptible to hydrolysis when trace amounts of water are unavoidably present in the coating composition. Therefore, the polysilazane compound, polysiloxane compound, and polysiloxane resin of the general formula 1, formula 2, or formula 3 are the best choices for the organosilicon compound B) containing oxygen or nitrogen. And R 1 is a group selected from the group consisting of: H, C 1 -C 18 alkyl, C 5 -C 6 -cycloalkyl, substituted or unsubstituted phenyl, OH, OC 1 -C 18 alkyl, NH 2 and N (C 1 -C 18 alkyl) 2 ; R 2 , R 3 and R 5 are each independently a group selected from the group consisting of: H, C 1- C 18 alkyl, OH, OC 1 -C 18 alkyl, NH 2 , N (C 1 -C 18 alkyl) 2 , OSi (R 1 ) 3 and N = SiR 1 ; R 4 is selected from the group consisting of The groups of the group: H, C 1 -C 18 alkyl, C 5 -C 6 -cycloalkyl and phenyl; X is O or N; and m and n are independently of each other and are selected from 1 Integer number in the range of 100; prerequisite is that the boiling point of each material exceeds 150 ° C. For example, Durazan 1066 (CAS-No. 346577-55-7) or polydimethylsiloxane (CAS-No. 9016-00-6) can be advantageously used as an oxygen or nitrogen-containing material in the present coating composition. Organic Si compound B). In addition, the silsesquioxane polymers of the general formula 4 are also advantageously useful: R 1 and R 2 are the same or different groups from each other and are selected from the group consisting of hydrogen, alkyl, olefin, cycloalkyl, aryl, arylene and alkoxy, and m and n are independently of each other an integer selected from a number ranging from 1 to 100, a prerequisite is that the boiling point of each material exceeds 150 ° C. Furthermore, in addition to the organic Si compound containing oxygen or nitrogen, an organic compound selected from the group consisting of Ge, Nb, Sn, Zr, Ti, Sb, Al, Bi, an alkali metal and / or an alkaline earth metal It may also be present in the coating composition of the present invention. These organic compounds may be alkoxides, carboxylates, citrates, acetamidine pyruvate, and / or tartrate of the corresponding elements. The organic compound, if any, is present in the coating composition in an amount of 1 to 30% by weight based on the total weight of the compound of component B). In particular, the amount of the organic alkali metal compound and / or the amount of the organic alkaline earth metal compound should not exceed 10% by weight based on the total weight of the component B). Preferably, the alkoxide of formula 5 is suitable: Met is selected from the group consisting of: Ge, Nb, Sn, Zr, Ti, Sb, Al, Bi, alkali metals and alkaline earth metals, and Z is selected from the group consisting of: CO, SO 2 and SO 3 ; P is 0 or 1, R 6 is a group selected from the group consisting of: C 1 -C 18 alkyl, C 5 -C 6 -cycloalkyl and substituted or unsubstituted benzene base. The coating composition according to the present invention also contains 5 to 25% by weight, preferably 5 to 15% by weight of the binder based on the total weight of the coating composition. Unexpectedly, the inventors of the present case found an adhesive that contains at least one compound selected from the group of polyvinyl acetals, and is able to provide this type of coating that can be advantageously used for several printing methods and coating methods.组合 物。 Composition. The adhesive largely determines the viscosity of the coating composition during the printing process. Although the viscosity of the coating composition must be low enough to be suitable for printing or coating in various printing methods or coating methods, individual coatings or printed layers must remain stable on the substrate after application without dispersing beyond the Coated surface area. In addition, the adhesive must be completely burnt after heat-treating the resulting coating or printed layer within the application range of the coating composition. The group of polyvinyl acetals meets these requirements of the coating composition. Polyvinyl acetals are polyvinyl formaldehyde, polyvinyl acetaldehyde, and polyvinyl butyral. The characteristics of polyethylene acetals change with the degree of acetalization. Polyvinyl butyral is the best choice for this coating composition. Therefore, polyvinyl butyraldehydes are preferable as a binder in the present coating composition. Particularly useful are polyvinylbutyraldehydes having an OH content of 18 to 24% by weight. Kuraray's polyvinyl butyraldehydes (sold under the trademarks Mowital® and Pioloform®) can be advantageously used, in particular having an average molar mass of about 40.000 g / mol and about 55.000 g / mol, respectively, and each exhibiting about 70 Mowital® B 45 H and Mowital® B 60 H with glass transition temperature of ℃, and Mowital® B 60 H is preferred. It goes without saying that another company's polyvinyl butyraldehydes which have considerable properties are also useful. The polyvinyl acetal-containing adhesive may contain at least 50% by weight of polyvinyl acetal based on the total weight of the adhesive, or may be composed of at least one compound selected from the group of polyvinyl acetals. Preferably, the adhesive comprises polyvinyl butyral. In a preferred embodiment of the present invention, the adhesive is composed of polyvinyl butyraldehyde. Most preferably, the adhesive is composed of polyvinyl butyraldehyde having an average molar mass in the range of 30.000 to 60.000 g / mol and an OH content of 18 to 24% by weight. The coating composition of the present invention further contains 10 to 70% by weight, preferably 40 to 70% by weight, of a solvent. The solvent is advantageously an organic solvent. Unfortunately, trace amounts of water may generally not be avoided to reach levels equal to zero, although the solvent in the present coating composition preferably contains only organic solvents. Therefore, the organic solvent used in the coating composition may contain water at a content of 0 to 10% by weight based on the weight of the solvent. In the case where an organic solvent mixture is used, it is preferable that various organic solvents may have a water content in the range of 0 to 10% by weight based on the weight of the various organic solvents, so that the maximum water amount in the solvent mixture does not More than 10% by weight. In the case of a single organic solvent or a mixture of organic solvents, as the case may be, the water content is preferably 0 to 5% by weight, more preferably 0 to 3% by weight, for each single organic solvent used. In principle, all organic solvents that can dissolve solid compounds (except metal particles) and evaporate at the temperature of the resulting coating that is heat-treated on a silicified substrate without residues can be used in the coating composition. Examples are alcohols such as ethanol, isopropanol, hexanol or 2-ethylhexanol, ethoxyethanol, methoxyethanol, methoxypropanol, and mixtures of at least two of the foregoing alcohols. In addition, polyether ethers are particularly useful, especially tri-propylene glycol-monomethyl ether (TPM) and di-propylene glycol-monomethyl ether (DPM). Most preferred are 2-ethylhexanol, tri-propylene glycol-monomethyl ether (TPM) and di-propylene glycol-monomethyl ether (DPM). All solvents can be used as sole solvents or as a mixture containing several solvents. Optionally, non-alcoholic solvents may also be present in the solvent mixture in an amount of 1 to up to 40% by weight based on the weight of the solvent mixture, such as, but not limited to, ethers like dialkylpropylene glycol, dioxane or THF, aromatic Solvents are like xylenes, saturated and unsaturated aliphatic hydrocarbons are like terpenes, solvents are petroleum naphtha, amines are like N-ethylpyrrolidone, and esters are like ethyl benzoate or fatty esters. By changing the amount of the solvent, the viscosity of the coating composition according to the present invention can be adjusted to a value that is useful and suitable for the corresponding coating technology or printing technology. A great advantage of the present invention is that the coating composition can be used in several coating techniques or printing techniques, thereby producing a thick coating composition that can be diluted to the required value by simply adjusting the solvent content, It is therefore useful for several coating techniques or printing techniques, including inkjet printing. In addition to the above-mentioned essential ingredients, the coating composition of the present invention may optionally include a rheology modifier in a case where the viscosity of the coating composition must be further adjusted in a very specific manner. The rheology modifier may be present in an amount of 0 to 10% by weight based on the weight of the coating composition. Preferably, an amount of 0 to 8% by weight, in particular 0 to 5% by weight, is used. The rheology modifier used in the coating composition can be selected from the group consisting of pine oil, castor oil, fatty acids, fatty acid derivatives, and natural or synthetic waxes. Examples of fatty acids are linoleic acid, oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, and capric acid. Fatty acid derivatives are also useful. Examples of natural waxes and synthetic waxes are C 19 to C 30 hydrocarbon montan wax, canauba wax, tan wax, collophonium wax like rosin acid or rosin, or polymer wax. Olefin waxes like Clariant's Ceridust® wax. In addition, the coating composition according to the present invention may optionally contain at least one metal salt compound, wherein the metal salt is selected from the group consisting of: Co, Ni, Cu, Cr, Fe, Mn, Au, Rh , Ru, Ir, Os and Pt. The metal salt compound may be present in an amount of 0 to 5% by weight, preferably 0 to 3% by weight, and particularly 0.1 to 1.5% by weight based on the weight of the coating composition. The metal salt has the following functions: adjusting the color of the obtained metal layer in the obtained coated product, and / or promoting adhesion of each coating composition to the substrate in a subsequent coating step. The metal salt is decomposed into the corresponding metal oxide and / or metal under the final heat treatment of the coating composition on the coated substrate. Preferably, organometallic salts are used in the coating composition according to the present invention. Examples are resinates, sulfuroresinates, thiolates, carboxylates, and alkoxides. The metal salt is usually used in the form of a solution of any of the above-mentioned organic solvents. It goes without saying that in the case where all the weight percentages mentioned above refer to the components A) to F) of the above coating composition, they refer to the total weight of the coating composition added to 100% by weight. In addition, the coating composition according to the present invention may contain additional additives, such as surfactants, defoamers, organic pigments and fillers, and other thixotropy, which are commonly used to produce metal coatings on siliconized substrates. Agent. In the case of using additional additives, the weight percentages of these additives are also selected to the extent that the sum of components A) to F) and the additional additives is added to 100% by weight. The present invention also relates to a method for producing the above-mentioned coating composition, in which the compounds A) to F) are uniformly mixed with each other, thereby achieving a ready-to-use coating composition. Preferably, a solution of the binder is prepared and other components are continuously added (preferably mixed with one or more of the solvents). If necessary, one or more of the above-mentioned additional additives may also be added. The mixing is preferably performed at ambient temperature using a rotor-stator homogenizer or Speedmixer®. In some cases, outgassing may be important, depending on the amount and type of solvent used. One of the great advantages of the present invention is that the method for producing the above-mentioned coating composition is as simple as possible. Mixing the components alone is sufficient to achieve a stable coating composition that can be stored in a closed container for at least six months without degradation, decomposition or settling of the solid components. Depending on the content of the solvent, rheology modifier and / or other thixotropic agent used, the coating composition can be used in different coating methods or printing methods (including inkjet printing method). Therefore, the thick coating composition can be applied by customers in several coating methods or printing methods, and since the content of the solvent can be adjusted later at the customer. The present invention also relates to the use of the above-mentioned coating composition, which is used for manufacturing a metal, gold, or Silver decorative elements. In order to achieve such metal elements on a silicified surface as described above, the coating composition according to the present invention must be applied to the silicified surface of an object and then further processed. The invention therefore also relates to a method for producing a metal-containing coating on a substrate, whereby a coating composition constituted as described above is applied to the substrate and subsequently in the range of 500 ° C to 1250 ° C Processing at medium temperature. This treatment is performed in an atmosphere containing oxygen. According to the present invention, the substrate having the silicified surface is an object exhibiting a surface of porcelain, china, bone china, ceramics, glass, or enamel. There is no limit to the kind of object itself. In principle, it is possible to use all articles which are rich in decoration or function by having a metal layer of the metal mentioned by the compound A) of the present coating composition on its surface. Examples are tiles, building elements, glass and porcelain for home or professional applications. The coating composition can be applied to the surface of the substrate directly or by means of a transfer medium. Direct application can be performed by any method familiar to those skilled in the art. Applying the coating composition to the substrate can be performed by immersing the substrate in the coating composition or by any coating method or printing method, such as a curtain coating method , Roller coating method, spin coating method, impregnation method, pouring method, drip coating method, spray method, spray method, doctor blade coating method, coating method or printing method, and the printing method may be inkjet printing method, screen printing method , Gravure printing method, lithographic printing method or pad printing method, and the painting method is a pen painting method, a brush painting method, and the like. The selection of the above coating method depends on the type and size of the substrate and the type of coating applied to the substrate. It goes without saying that the viscosity of the coating composition must be adjusted due to the required coating technique. Since the viscosity of the coating composition can be easily and variably adjusted by changing the amount of individual solvents in most cases, the thick coating composition according to the present invention can be used as a base composition for more than one application technique Thing. The preferred printing methods are screen printing, gravure printing, pad printing and inkjet printing. Printing methods by means of brushes or pens are also advantageously available. The application of the coating composition to the substrate can also be performed by a direct method, that is, the coating composition is applied to the transfer medium by a first step, and the second step The transfer medium of the coating composition of the invention applies the coating composition to the substrate. The transfer medium may be composed of a polymer or paper carrier that is pre-coated with the present coating composition and dried (for example, in a printed form). The coating composition is then applied to the substrate by positioning the pre-coated support on the substrate and removing the polymer or paper support. The heat treatment in this case is performed after the coating composition is applied to the substrate, rather than after the coating composition is applied to the polymer or paper support. The substrate can have any shape that allows the coating composition to be applied to the substrate. Flat substrates such as films, plates, and sheets are as useful as three-dimensional substrates of any shape, like a sphere or cone, or any other useful three-dimensional shape. The substrate may be a dense body or a hollow body, which has an outer and / or inner silicified surface covered with porcelain, china, bone china, ceramic, glass, or enamel covered with the coating composition of the present invention. The siliconized surface of the substrate preferably contains at least one continuous region on which the coating composition can be applied. The shape of the area covered by the coating composition may be any suitable shape in the following forms: regular or irregular patterns, lines, geometric shapes (such as circles, squares, rectangles, etc.), photos, signs, bar codes, and the like. The size and shape of the area of the substrate covering the coating composition is limited only by the type of coating method or printing method used and / or the geometry of the substrate itself. This coating method allows a pattern having a very fine wire diameter to be produced on the substrate. The size of the coated area is in the range of 0.5 mm 2 to 10 m 2 , especially in the range of 10 mm 2 to 5 m 2 , and most preferably in the range of 100 mm 2 to 1 m 2 . It can also be a wire diameter of 0.01 mm to 10 cm, especially 0.1 mm to 1 cm. A solid coating on the substrate is achieved when the coating method according to the invention is completed, wherein the coating contains a continuous dense metal layer comprising the nano metal mentioned under component A) of the coating composition Particles, and the nano metal particles are at least partially encapsulated by a glass matrix. This metal layer is covered by a glass top coat. The glass substrate and the glass topcoat contain metal oxides of the metals mentioned under component B) of the coating composition and optionally metal or metal oxides of the metals mentioned under component F). At least, the glass substrate and the glass topcoat contain a network made of silicon atoms and oxygen atoms. Residual nitrogen atoms may also be present. The top coat protects the metal layer and prevents its corrosion and / or mechanical or chemical decomposition, and the matrix encapsulating the metal particles enables the nano metal particles to adhere to the substrate. Although the coating composition according to the present invention is applied to the substrate and automatically includes a top coat that protects the metal layer as described above after heat treatment, it may be desirable or advantageous to have one or more additional protections Layer to cover the resulting solid coating. Therefore, the method optionally also includes a method step in which the coating composition containing metal particles can be further partially or completely covered with an additional protective layer. This method step can be carried out before the heat treatment of the layer stack, or even after heat treatment of the coating composition containing metal particles on the substrate. The invention also relates to a solid coating containing metal particles on a substrate, comprising at least 60% by weight of metal particles of at least one metal based on the weight of the solid coating, the at least one metal being selected from the group consisting of Group: Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or an alloy containing at least one of the above metals, and a glass matrix containing at least 5% by weight based on the weight of the solid coating, The glass matrix is composed of SiO 2 or contains SiO 2 and alkali metal oxide, alkaline earth metal oxide, GeO 2 , Nb 2 O 3 , SnO, SnO 2 , ZnO, ZrO 2 , TiO 2 , Al 2 O 3 , Bi 2 At least one of O 3 and Sb 2 O 3 . The metal particles are nano metal particles related to the coating composition as component A) described above. The content of the glass substrate is preferably within a range of 5 to 40% by weight, particularly within a range of 5 to 20% by weight based on the weight of the solid coating. Therefore, the amount of metal-containing particles in the solid coating containing metal particles on the substrate is preferably at least 80%, that is, in the range of 80 to 95% by weight of the total weight of the solid coating. It is advantageous if the glass substrate contains up to 5% by weight of alkali metal oxides and / or alkaline earth metal oxides based on the weight of the solid coating on the substrate, due to such low concentrations of alkali metal oxidation And / or alkaline earth metal oxides can improve the mechanical properties of the resulting coatings related to scratch resistance and durability associated with prolonged exposure to steam. If present, the decomposition products of the metal salts according to component F) of the coating composition are counted on the glass-based mass rather than on the metal-containing particles. Therefore, the glass matrix may additionally contain one or more metals or metal oxides, the metal being selected from the group consisting of Co, Ni, Cu, Cr, Fe, Mn, Au, Rh, Ru, Ir, Os, and Pt. Preferably, the glass matrix contains a metal or metal oxide of Cu, Au, Rh and / or Ru, which is derived from a component of compound F). In a preferred embodiment of the present invention, the metal particles in the solid coating containing metal particles on the substrate are composed of one or more precious metals selected from the group consisting of: Ag, Au , Ru, Ir, Pd, Pt, or an alloy containing at least one of the above noble metals. The best embodiment is that the solid coating containing metal particles on the substrate contains only silver metal particles or silver-containing alloy metal particles, and the alloy has a silver content of at least 50% by weight based on its weight . As explained above to a certain extent, the solid coating containing metal particles on the substrate is composed of two layers on top of each other, whereby the first layer is directly on the substrate and constitutes a densely packed metal layer , Which includes aggregated metal particles exhibiting a d 50 value in the range of 50 to 300 nm, which d 50 value is measured using a volume-dependent laser diffraction method, wherein the metal particles are selected from the group consisting of Group: Ag, Au, Ru, Ir, Pd, Pt, Cu, Nb, or an alloy containing at least one of the above metals, and wherein the second layer is above the first layer and is a glass-like sample containing at least SiO 2 Layer (glass-like layer). The densely packed metal layer constitutes a continuous layer, wherein the metal particles can still be considered as particles exhibiting a d 50 value in the range of 50 to 300 nm, but aggregated and partially fused together and at least partially by a glass matrix For encapsulation, the glass substrate is composed of the same components as the glass-like layer on the metal layer. A protective layer is located on the metal layer. The protective layer has a glass-like structure and is composed of a glass matrix containing only SiO 2 or a glass matrix containing SiO 2 and one or more metal oxides, the one or more metal oxides The substance is selected from the group: alkali metal oxide, alkaline earth metal oxide, GeO 2 , Nb 2 O 3 , SnO, SnO 2 , ZnO, ZrO 2 , TiO 2 , Al 2 O 3 , Bi 2 O 3 and Sb 2 O 3 . The protective layer, if present, may also contain decomposition products of component F), more precisely one or more metals or metal oxides selected from the group: Co, Ni, Cu, Cr, Fe, Mn, Au, Rh , Ru, Ir, Os, and Pt. In a preferred embodiment of the present invention, the solid coating on the substrate according to the present invention is composed of a metal layer directly on the substrate, which contains silver particles or has a weight based on the weight of the alloy. Based on at least 50% by weight of the silver-containing alloy particles, they exhibit a d 50 value in the range of 50 to 300 nm as described above, and a glass-like layer containing SiO 2 and rhodium over the metal layer. Based on the coating weight added to 100%, the amount of the metal (ie, Ag or Ag alloy) is at least 85% by weight, the amount of SiO 2 is at least 3% by weight, and the amount of rhodium is at most 0.5% by weight. . The glass-like layer as described above covers the metal layer and protects the metal layer from corrosion and mechanical or chemical decomposition. In addition, the glass-like layer provides some scratch resistance to the underlying metal layer. The protective properties of the glass-like layer are strong enough to prevent the silver nano-particles (usually susceptible to strong corrosion) from corroding. Thus, for the first time, silver nano particles can be used to produce a shiny silver decoration on ceramics, glass, tiles, etc., having a coating composition according to the present invention. The substrate having the solid coating thereon is an object exhibiting an outer silicified surface such as porcelain, china, bone china, ceramic, glass, or enamel surface. It goes without saying that the entire article may be composed of one of the above materials, but an article having only a siliconized surface, in which the article body is composed of different materials and should also be included in the present invention. Of course, the surface of the article and its body must withstand the temperatures of the heat treatments described above. There is no limit to the shape and size of the object itself. The silicified surface may be the outer surface or the inner surface of the object (for example, for a hollow object). The invention allows the silicified surface of an object to be coated with a flat or matte (as the case may be) metal layer in one coating step, which metal layer exhibits silver or gold color and is protected from chemical or mechanical decomposition or corrosion . Even the coating composition itself has a long storage life, that is, resistance to corrosion and decomposition for at least six months. The nano metal particles used can be made into a suitable size before use and do not have to produce the golden decoration on the silicided surface in situ on the covered surface as usual. Since even nano-silver particles are stable and particularly resistant to corrosion in this coating composition, silver (instead of palladium and platinum) can be used to produce silicified objects such as ceramics, glass and Tiles), thereby improving cost control in terms of generating individual goods. The present invention will be described in detail in the following embodiment, but should not be limited by this embodiment.